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CHM 321: Inorganic Chemistry

This is the LibreText Open Educational Resource (OER) book for the CHM 321: Inorganic Chemistry course at Ripon College.

Chemistry

Tác giả: Bryan P. Nell
Nhà xuất bản: Ripon College
Nguồn: LibreTexts
Giấy phép: CC BY-NC-SA
Ngôn ngữ: EN
Danh mục: Khoa học cơ bản

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Mục lục· 293 mục

01: Atomic Structure Molecular Structure and Bonding
1.01: Introduction to Inorganic Chemistry
1.1.01: What is Inorganic Chemistry
1.1.02: Inorganic vs Organic Chemistry
1.1.03: History of Inorganic Chemistry
1.02: Atomic Structure
1.2.01: Historical Development of Atomic Theory
1.2.1.01: The Periodic Table
1.2.1.02: Discovery of Subatomic Particles and the Bohr Atom
1.2.02: The Schrodinger equation particle in a box and atomic wavefunctions
1.2.2.01: Particle in a Box
1.2.2.02: Quantum Numbers and Atomic Wave Functions
1.2.2.03: Aufbau Principle
1.2.2.04: Shielding
1.2.03: Periodic Properties of Atoms
1.2.3.01: Ionization energy
1.2.3.02: Electron Affinity
1.2.3.03: Covalent and Ionic Radii
1.03: Rutherford's Atom
1.04: Bohr's Atom
1.05: Simple Bonding Theory
1.5.01: Lewis Electron-Dot Diagrams
1.5.1.01: Resonance
1.5.1.02: Breaking the octet rule with higher electron counts (hypervalent atoms)
1.5.1.03: Formal Charge
1.5.1.04: Lewis fails to predict unusual cases- Boron and Beryllium
1.5.02: Valence Shell Electron-Pair Repulsion
1.5.2.01: Lone Pair Repulsion
1.5.2.02: Multiple Bonds
1.5.2.03: Electronegativity and Atomic Size Effects
1.5.03: Molecular Polarity
1.5.04: Hydrogen Bonding
1.5.05: Valence Bond Theory
1.5.06: Hybrid Atomic Orbitals
1.06: Molecular Orbital Theory
1.6.01: Prelude to Molecular Orbital Theory
1.6.02: Formation of Molecular Orbitals from Atomic Orbitals
1.6.2.01: Molecular Orbitals from s Orbitals
1.6.2.02: Molecular Orbitals from p Orbitals
1.6.2.03: Molecular orbitals from d orbitals
1.6.2.04: Nonbonding Orbitals and Other Factors
1.6.03: Homonuclear Diatomic Molecules
1.6.3.01: Molecular Orbitals
1.6.3.02: Orbital Mixing
1.6.3.03: Diatomic Molecules of the First and Second Periods
1.6.3.04: Photoelectron Spectroscopy
1.6.04: Heteronuclear Diatomic Molecules
1.6.4.01: Polar bonds
1.6.4.02: Ionic Compounds and Molecular Orbitals
02: Molecular Symmetry and Group Theory
2.01: Symmetry Elements and Operations
2.02: Point Groups
2.2.01: Groups of Low and High Symmetry
2.2.02: Other Groups
2.03: Properties and Representations of Groups
2.3.01: Matrices
2.3.02: Representations of Point Groups
2.3.03: Character Tables
2.04: Examples and Applications of Symmetry
2.4.01: Molecular Vibrations
2.4.02: Chirality
2.05: Generating SALCs for Polyatomic Molecules
2.5.01: Bifluoride anion
2.5.02: Carbon Dioxide
2.5.03: HO
2.5.04: NH
2.5.05: CO (Revisted with Projection Operators)
2.5.06: BF
03: Acid-Base Chemistry and an Introduction to Coordination Compounds
3.01: Bronsted-Lowry acids and bases
3.02: Lewis Acids and Bases
3.03: Acidity of the Hexaaqua Ions
3.04: Hard Soft Acids and Bases
3.05: Quantitative Measures of Hardness and Softness
3.06: Coordination Chemistry- Structure and Isomers
3.6.01: History
3.6.02: Nomenclature and Ligands
3.6.03: Acid-Base and Donor-Acceptor Chemistry
3.6.3.01: Acid-Base Models as Organizing Concepts
3.6.3.02: Lewis Concept and Frontier Orbitals
3.6.3.2.01: The frontier orbital approach considers Lewis acid-base reactions in terms of the donation of electrons from the base's highest occupied orbital into the acid's lowest unoccupied orbital.
3.6.3.2.02: All other things being equal electron withdrawing groups tend to make Lewis acids stronger and bases weaker while electron donating groups tend to make Lewis bases stronger and acids weaker
3.6.3.2.03: The electronic spectra of charge transfer complexes illustrate the impact of frontier orbital interactions on the electronic structure of Lewis acid-base adducts
3.6.3.2.04: Substances' solution phase Lewis basicity towards a given acid may be estimated using the enthalphy change for dissociation of its adduct with a reference acid of similar hardness.
3.6.3.2.05: In the boron trifluoride affinity scale the enthalphy change on formation of an adduct between the base and boron trifluoride is taken as a measure of Lewis basicity.
3.6.3.2.06: Lewis base strength may also be estimated by measuring structural or energy changes upon formation of a Lewis acid-base complex as illustrated by efforts to spectroscopically assess the strengths of halogen bonds
3.6.3.2.07: Bulky groups weaken the strength of Lewis acids and bases because they introduce steric strain into the resulting acid-base adduct.
3.6.3.2.08: Frustrated Lewis pair chemistry uses Lewis acid and base sites within a molecule that are sterically restricted from forming an adduct with each other.
3.6.3.03: Hard and Soft Acids and Bases
3.6.3.3.01: Hard-Hard and Soft-Soft preferences may be explained and quantified in terms of electrostatic and covalent and electronic stabilization on the stability of Lewis acid-base adducts
3.6.3.3.02: Quantitative Measures of Hardness Softness and Acid-Base Interactions from a Hard Soft Acid-Base Principle Perspective Involve Orbital Energies and or Apportioning Acid-Base Bonding in Terms of Electrostatic and Covalent Factors
3.6.3.04: Problems
3.6.04: Coordination Numbers and Structures
3.6.05: Isomerism
3.07: Coordination Chemistry- Bonding
3.7.01: Crystal Field Theory
3.7.02: Crystal Field Stabilization Energy
3.7.03: Factors That Affect Crystal Field Splitting
3.7.04: Ligand Field Theory
3.7.05: Metal-Metal Bonds
3.7.5.01: Metal-Metal Multiple Bonds
3.7.06: Jahn-Teller Distortions
04: Electronic Structure and Spectra of d-Metal Complexes
4.01: Absorption of Light
4.1.01: Beer-Lambert Absorption Law
4.02: Quantum Numbers of Multielectron Atoms
4.2.01: Finding Microstates and Term Symbols
4.2.02: Spin-Orbit Coupling
4.03: Electronic Spectra of Coordination Compounds
4.3.01: Symmetry labels for split terms
4.3.02: Correlation Diagrams
4.3.03: Tanabe-Sugano Diagrams
4.3.04: Applications of Tanabe-Sugano Diagrams
4.3.05: Tetrahedral Complexes
4.3.06: Selection Rules
4.3.07: Charge-Transfer Spectra
4.3.08: Applications of Charge-Transfer
05: Reactions of d-Metal Complexes
5.01: Thermodynamic Stability of Metal Complexes
5.02: Trends in Kinetic Lability
5.03: Ligand Substitution Mechanisms
5.04: Substitutions in Square Planar Complexes
5.4.01: Kinetics and Stereochemistry of Square Planar Reactions
5.4.02: Evidence for Associative Reactions
5.05: The Trans Effect Observation
5.06: The Trans Effect Explanation
5.07: Redox Mechanisms
5.7.01: Outer Sphere Electron Transfer
5.7.02: Inner Sphere Electron Transfer
06: Organometallic Chemistry
6.01: Introduction to Organometallic Chemistry
6.02: Nomenclature Ligands and Classification
6.03: Electron Counting in Organometallic Complexes
6.3.01: The 18 Electron Rule
6.3.02: Simplifying the Organometallic Complex by Deconstruction
6.04: Survey of Organometallic Ligands
6.4.01: Carbon Monoxide (Carbonyl Complexes)
6.4.02: Ligands similar to CO
6.4.03: Hydrides and Dihydrogen Complexes
6.05: Bonding between Metal Atoms and Organic Pi Systems
6.5.01: Linear Systems
6.5.02: Cyclic systems
6.5.03: Odd-numbered Systems
6.5.04: Fullerene Complexes
6.06: Metal-Carbon Bonds
6.6.01: Metal Alkyls
6.6.02: Carbenes
6.6.03: Carbyne (Alkylidyne) Complexes
6.6.04: Carbido and Cumulene Complexes
6.6.05: Carbon Wires- Polyyne and Polyene Bridges
6.07: Characterization of Organometallic Complexes
07: Organometallic Reactions and Catalysis
7.01: Reactions Involving Gain or Loss of Ligands
7.1.01: Ligand Dissociation and Substitution
7.1.02: Oxidative Addition
7.1.03: Reductive Elimination
7.1.04: Sigma Bond Metathasis
7.1.05: Application of Pincer Ligands
7.02: Reactions Invloving Modification of Unsaturated Ligands
7.2.01: Introduction to Insertion
7.2.02: CO Insertions (Alkyl Migration)
7.2.03: Migratory Insertion-12-Insertions
7.2.04: -Elimination Reactions
7.2.05: Abstraction and Addition
7.03: Organometallic Catalysts
7.3.01: Catalytic Deuteration
7.3.02: Hydroformylation
7.3.03: Monsanto Acetic Acid Process
7.3.04: Wacker (Smidt) Process
7.3.05: Hydrogenation by Wilkinson's Catalyst
7.3.06: Olefin Metathesis
7.04: Heterogeneous Catalysts
7.4.01: Ziegler-Natta Polymerizations
7.4.02: Water-Gas Shift Reaction
7.05: Problems
7.5.01: Concept Review Questions Chapter 12
7.5.02: Homework Problems Chapter 12
08: Solid State Chemistry
8.01: Prelude to Metals and Alloys
8.02: Unit Cells and Crystal Structures
8.03: Crystal Structures of Metals
8.04: Conduction in Metals
8.05: Atomic Orbitals and Magnetism
8.06: Ferro- Ferri- and Antiferromagnetism
8.07: Hard and Soft Magnets
8.08: Defects in Metallic Crystals
8.09: X-ray Crystallography
8.10: Miller Indices (hkl)
8.11: Powder X-ray Diffraction
8.12: Prelude to Ionic and Covalent Solids - Structures
8.13: Close-packing and Interstitial Sites
8.14: Structures Related to NaCl and NiAs
8.15: Tetrahedral Structures
8.16: Layered Structures and Intercalation Reactions
8.17: Ionic Radii and Radius Ratios
8.18: Structure Maps
8.19: Energetics of Crystalline Solids- The Ionic Model
8.20: Born-Haber Cycles for NaCl and Silver Halides
8.21: Lattice Energies and Solubility
8.22: Spinel Perovskite and Rutile Structures
8.23: Kapustinskii Equation
8.24: New Page
09: Bioinorganic Chemistry
9.01: Biological Significance of Iron Zinc Copper Molybdenum Cobalt Chromium Vanadium and Nickel
9.02: Introduction to Amino Acids and Proteins
9.03: Overview of Hemoglobin and Myoglobin
9.3.01: Myoglobin Hemoglobin and their Ligands
9.3.02: Oxygen Transport by the Proteins Myoglobin and Hemoglobin
9.04: Ferrodoxins Hydrogenases and Nitrogenases - Metal-Sulfide Proteins
9.4.01: Iron-sulfur Proteins and Models
9.4.02: Iron-sulfur Proteins and Models (Part 2)
9.4.03: Iron-sulfur Proteins and Models (Part 3)
9.4.04: Iron-sulfur Proteins and Models (Part 4)
9.05: The Reaction Pathways of Zinc Enzymes and Related Biological Catalysts
9.5.01: About Carbonic Anhydrase
9.5.02: Catalytic Mechanism
9.5.03: Metal Substitution
9.06: Metals in Medicine
9.6.01: Metal Deficiency and Disease
9.6.02: Toxic Effects of Metals
9.6.03: Aspects of Platinum Binding to DNA
9.6.04: Survey of Metals Used for Diagnosis and Chemotherapy
9.6.05: Platinum Anticancer Drugs- A Case Study
9.6.06: Mapping the Major Adducts ofcis-andtrans-DDP on DNA Sequence Specificity
9.6.07: Structure of Platinum-DNA Complexes
9.6.08: Site-specifically Platinated DNA (154)
9.6.09: Bioinorganic Chemistry of Platinum Anticancer Drugs- How Might They Work
9.6.10: Bioinorganic Chemistry of Platinum Anticancer Drugs How Might They Work (Part 2)
9.6.11: Design of New Inorganic Anticancer Drugs
9.07: Electron Transfer
10: Special Topics
10.01: f-Block Metals- Lanthanides and Actinides
10.1.01: Introduction
10.1.02: f-Orbitals and Oxidation States
10.1.03: Atoms and Ion Sizes
10.1.3A: The Lanthanoid Contraction
10.1.3B: Coordination Numbers
10.1.04: Spectroscopic and Magnetic Properties
10.1.4A: Electronic Spectra and Magnetic Moments - Lanthanoids
10.1.4B: Luminescence of Lanthanoid Complexes
10.1.4C: Electronic Spectra and Magnetic Moments - Actinoids
10.1.05: Sources of the Lanthanoids and Actinoids
10.1.5A: Occurrence and Separation of the Lanthanoids
10.1.5B: The Actinoids
10.1.06: Lanthanoid Metals
10.1.07: Inorganic Compounds and Coordination Complexes of the Lanthanoids
10.1.7A: Halides
10.1.7B: Hydroxides and Oxides
10.1.7C: Complexes of Ln(III)
10.1.08: Organometallic Complexes of the Lanthanoids
10.1.8A: (sigma)-Bonded Complexes
10.1.8B: Cyclopentadienyl Complexes
10.1.8C: Bis(arene) Derivatives
10.1.8D: Complexes Containing the (eta8)-cyclooctatetraenyl Ligand
10.1.09: The Actinoid Metals
10.1.10: Inorganic Compounds and Coordination Complexes of Thorium Uranium and Plutonium
10.1.10A: Thorium
10.1.10B: Uranium
10.1.10C: Plutonium
10.1.11: Organometallic Complexes of Thorium and Uranium
10.1.11A: (sigma)-Bonded Complexes
10.1.11B: Cyclopentadienyl Derivatives
10.1.11C: Complexes Containing the (eta8)-cyclooctatetraenyl Ligand
10.02: Physical Inorganic Techniques
10.2.01: Electronic Spectroscopy
10.2.1A: UV-VIS Absorption Spectroscopy
10.2.1B: Types of Absorption
10.2.1C: Absorbance and the Beer-Lambert Law
10.2.1D: Emission Spectroscopy
10.2.02: Nuclear Magnetic Resonance (NMR) Spectroscopy
10.2.03: Electron Paramagnetic Resonance (EPR) Spectroscopy
10.2.3A: What is EPR Spectroscopy
10.2.3B: The Zeeman Electronic Effect
10.2.3C: EPR Spectra
10.2.04: Mossbauer Spectroscopy
10.2.4A: The Technique of Mossbauer Spectroscopy
10.2.4B: What Can Isomer Shift Data Tell Us
10.2.05: Structure Determination - Diffraction Methods
10.2.5A: X-Ray Diffraction (XRD)
10.2.5B: Single Crystal X-Ray Diffraction
10.2.5C: Powder X-Ray Diffraction
10.2.5D: Single Crystal Neutron Diffraction
10.2.5E: Electron Diffraction
10.2.5F: Low-Energy Electron Diffraction (LEED)
10.2.5G: Structural Databases
10.2.06: Photoelectron Spectroscopy (PES UPS XPS ESCA)
10.2.07: Mass Spectrometry
10.2.7A: Electron Ionization (EI)
10.2.7B: Fast Atom Bombardment (FAB)
10.2.7C: Matrix-Assisted Laser Desorption Ionization Time-of-Flight (MALDI-TOF)
10.2.7D: Electrospray Ionization (ESI)
10.03: Fluxional Behavior
10.3.01: Determination of Energetics of Fluxional Molecules by NMR